laser-induced breakdown spectroscopy; phosphate rocks; organomineral fertilizers; principal components analysis; partial least squares regression;ELEMENTAL ANALYSIS; PLANT MATERIALS; SOIL; CHEMOMETRICS

A number of phosphate rocks and organomineral P fertilizers was analyzed comparatively by laser-induced breakdown spectroscopy (LIBS) in both single- and double-pulse modes associated with two chemometric methods, i.e., principal components analysis (PCA) and partial least squares regression (PLSR). PCA was demonstrated to be a valuable method for the identification of spectral differences between similar samples with only minor compositional differences. The raw and normalized LIBS spectra were able to provide effective identification and discrimination at a 95% confidence level and in good agreement with the reference concentrations. Results obtained confirm the promising potential of LIBS for the rapid classification of P fertilizers in situ.

INDUCED BREAKDOWN SPECTROSCOPY; OPTICAL-EMISSION-SPECTROMETRY; TRACE-ELEMENTS; MICRONUTRIENTS; MEMBRANE; CADMIUM; WATER

A novel calibration method was developed for the determination of macronutrients in suspension fertilizer samples by laser-induced breakdown spectroscopy(LIBS). The fertilizer samples were mixed with 10% m/v polyvinyl alcohol (PVA) and dried for approximately 2 h at 50 degrees C, resulting in a solid polymer film with the immobilized liquid sample. This study describes the use of LIBS and 12 normalization strategies to determine Cu, K, Mg, Mn and Zn as well as As, B, Ca, Cd, Cr, Fe, Na, P and Pb in suspension fertilizers by inductively coupled plasma optical emission spectrometry (ICP OES) and inductively coupled plasma mass spectrometry (ICP-MS) analyses. LIBS equipment parameters were chosen following optimization with a Doehlert design. The results clearly demonstrate a good agreement between the LIBS predicted concentrations and the reference concentrations determined by ICP OES after microwave-assisted acid digestion (AOAC 2006.03 Official Method). Correlations of R-2 = 0.9958, 0.9489, 0.9992, 0.9968 and 0.9809 for Cu, K, Mn, Mg and Zn, respectively, were obtained. Significant levels of potentially toxic elements such as 10 mg L-1 As, 4.0 mg L-1 Cd, 8.0 mg L-1 Cr and 20 mg L-1 Pb were detected after ICP-MS analysis. The results with low standard errors of prediction for LIBS (from 0.02 to 0.06%) indicate that this proposed suspension sample preparation procedure exhibits significant potential for the development and implementation of methods for determining essential nutrients in suspension fertilizers and other samples for which mineralization is difficult.

Biochar-based fertilizers; Calcium; Libs; Internal standardization;SPECTROMETRY; SOILS; COAL

Biochar has gained agricultural importance as a soil amendment because of its important agricultural properties such as water retention, plant nutrient supplier, promoter of microorganism growth, sequestration action of atmospheric CO2, etc. Further, it is a low cost material being produced by recycling. Due to its active sites, biochar can adsorb nutrients so acting as a soil fertilizer. Thus the rapid assessment of nutrients in these materials is essential to ensure quality control for agricultural purposes. This work aimed to develop a simple analytical method based on Laser-Induced Breakdown Spectroscopy (LIBS) to determine Ca in biochar-based fertilizers. In particular, biochar samples enriched with Ca were prepared from peanut shells, residues of eucalyptus and banana fibers. The calibration standards were prepared by matrix matching using a biochar from eucalyptus residues. Different spectral preprocessing were evaluated to enhance the precision and accuracy of the method. However, the matrix effects demanded the use of internal standardization as the appropriate methodology to obtain the best accuracy. A linear correlation coefficient of 0.989 and a linear work range of 1.51-11.23% Ca were obtained using the proposed method, which yielded limits of detection and quantification of 0.45% e 1.51%, respectively. Calcium contents determined by LIBS in biochar-based fertilizers were in good agreement (paired t-test at 95% confidence level) with those determined by using High-Resolution Continuous Source Atomic Absorption Spectrometry (HR-CS FAAS) as the reference technique. Thus, the importance of internal standardization was demonstrated to be successful for the quantitative analysis of Ca in complex matrices like biochar-based fertilizers. (C) 2017 Elsevier B.V. All rights reserved.

Soil; Plant; Fertilizer; DP LIBS analysis; Orthogonal geometry; Ablative energy;SIGNAL ENHANCEMENT; PLANT MATERIALS; PLASMA; LIBS; FERTILIZERS; ABLATION; SOILS; QUANTIFICATION; CONTAMINANTS; DEPENDENCE

A soil, a plant and a fertilizer sample were investigated by double-pulse (DP) laser-induced breakdown spectroscopy (LIBS) in orthogonal beam geometry using a reheating configuration. The DP-LIBS signal enhancement was evaluated with respect to the corresponding single-pulse (SP) LIBS as a function of the interpulse delay at various ablation energies. The maximum signal enhancement measured was 155-fold when low ablation energy (4 mJ) and an interpulse delay of 10 mu s were used. At high laser energies (>= 16 mJ) and interpulse delay of 0.6 mu s, the maximum signal enhancement was up to 3-fold. The effect of excitation energies and interpulse delays on emission line intensities was discussed in the various conditions used. The emission line enhancement measured for ionic lines was always higher than that of atomic lines. Plasma excitation temperature and electron density measured as a function of interpulse delays at various ablation energies were shown to be related to the emission line intensities. (C) 2017 Elsevier B.V. All rights reserved.